TW201940225A - Water system ORP monitor and/or control method, and water treatment method and device - Google Patents

Water system ORP monitor and/or control method, and water treatment method and device Download PDF

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TW201940225A
TW201940225A TW108110115A TW108110115A TW201940225A TW 201940225 A TW201940225 A TW 201940225A TW 108110115 A TW108110115 A TW 108110115A TW 108110115 A TW108110115 A TW 108110115A TW 201940225 A TW201940225 A TW 201940225A
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redox potential
water
value
water system
orp
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亀田英邦
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日商栗田工業股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

A water system ORP monitor and/or control method to monitor and/or control ORP of a water system, wherein the ORP and pH of the water system are measured, a measured ORP value is corrected to an ORP value at standard conditions on the basis of a preset correction equation that is based on measured ORP and pH values, and the ORP of the water system is monitored and/or controlled on the basis of the corrected ORP value. The corrected ORP value is calculated from the measured ORP and pH values on the basis of the following equation. Corrected ORP value (mV) = measured ORP value (mV)-59*(7- measured pH value).

Description

水系統的ORP監測和/或控制方法以及水處理方法和裝置ORP monitoring and / or control method for water system and water treatment method and device

本發明是有關於一種準確掌握並監測及/或控制水系統的氧化還原電位（Oxidation-Reduction Potential，ORP）值的方法。另外，本發明是有關於一種利用所述水系統的ORP監測及/或控制方法的水處理方法和裝置以及逆滲透膜處理方法。The invention relates to a method for accurately grasping and monitoring and / or controlling an oxidation-reduction potential (ORP) value of a water system. In addition, the present invention relates to a water treatment method and device and a reverse osmosis membrane treatment method using the ORP monitoring and / or control method of the water system.

本發明中，所謂「ORP」是「氧化還原電位」，另外，所謂「RO供水」是指導入至逆滲透（Reverse Osmosis，RO）膜裝置並進行了RO膜處理的水，通常相當於RO膜裝置的入口水。以下，有時將「監測及/或控制」記載為「監測·控制」。In the present invention, the "ORP" means "redox potential", and the "RO water supply" refers to water that has been guided to a reverse osmosis (RO) membrane device and has undergone RO membrane treatment, and is generally equivalent to an RO membrane Appliance inlet water. Hereinafter, "monitoring and / or control" may be described as "monitoring and control".

於以井水、工業用水、自來水等為原水的用水處理或以含有有機物的排水等為原水的排水回收系統中，於原水中添加凝聚劑，使原水中的懸濁物質、膠體成分或有機物質等凝結且粗大化。繼而，於進行利用沈澱、浮起、過濾、膜過濾等進行固液分離的前處理後，或者於進行單獨利用膜過濾來除濁·除菌的前處理後，進行RO膜處理。Adding a coagulant to raw water in a wastewater treatment system using well water, industrial water, tap water, etc. as raw water, or drainage containing organic matter as raw water, to make suspended substances, colloidal components or organic substances in raw water Wait for condensation and coarsening. Then, after performing a pretreatment for solid-liquid separation using precipitation, floating, filtration, membrane filtration, or the like, or after performing a pretreatment for removing turbidity and sterilization by membrane filtration alone, RO membrane treatment is performed.

於這樣的用水處理或排水回收系統中，特別是於以含有有機物的排水為原水的情況下，將利用前處理而未完全去除的有機物作為營養源，於裝置配管內或RO膜面上活菌增殖，有時會引起膜的透過水量的下降。因此，採用在導入至RO膜裝置的RO供水中持續或間歇地添加氧化劑而抑制膜堵塞的對策。In such a water treatment or drainage recovery system, especially when the drainage containing organic matter is used as raw water, the organic matter that has not been completely removed by the pretreatment is used as a nutrient source, and live bacteria are in the pipe of the device or on the surface of the RO membrane. Proliferation may cause a decrease in the amount of water permeated through the membrane. Therefore, a countermeasure for suppressing membrane blocking by continuously or intermittently adding an oxidant to the RO water supply to the RO membrane device is adopted.

通常，於前處理設備中，利用次氯酸鈉或二氧化氯等游離氯系的氧化力高的氧化劑進行殺菌。聚醯胺系的RO膜對所述氧化力高的氧化劑的耐性低，因此於RO膜的前段注入亞硫酸氫鈉等的還原劑而還原去除游離氯，其後，添加氯胺或氯胺磺酸鈉等結合氯系氧化劑或含有異噻唑啉酮系化合物等地抑制細菌增殖的化合物的黏泥控制劑（slime control agent），從而抑制RO膜污染（專利文獻1、專利文獻2）。Generally, in a pretreatment facility, sterilization is performed using an oxidizing agent having a high oxidizing ability of free chlorine such as sodium hypochlorite or chlorine dioxide. The polyamine-based RO film has low resistance to the oxidizing agent having a high oxidizing power. Therefore, a reducing agent such as sodium bisulfite is injected into the front stage of the RO film to reduce and remove free chlorine. Then, chloramine or chloramine sulfonate is added. A slime control agent that combines a chlorine-based oxidant or an isothiazolinone-based compound with a compound that inhibits the proliferation of bacteria to suppress RO membrane fouling (Patent Document 1, Patent Document 2).

於使用含有高濃度有機物的排水作為原水的排水回收中，若僅藉由利用結合氯系氧化劑或異噻唑啉酮系化合物等的抑制技術，則有時無法抑制RO膜中的細菌增殖而導致膜堵塞。因此，理想的是對RO膜的前段的還原劑的添加量進行高度控制，而殘留不會導致膜劣化的程度的游離氯系氧化劑。In waste water recovery using waste water containing a high concentration of organic matter as raw water, if only a suppression technology combining a chlorine-based oxidizing agent or an isothiazolinone-based compound is used, it may not be possible to suppress the proliferation of bacteria in the RO membrane and cause the membrane Clogged. Therefore, it is desirable to control the addition amount of the reducing agent in the front stage of the RO membrane to a high degree while leaving free chlorine-based oxidants to such an extent that the membrane does not deteriorate.

先前，已知基於ORP值進行氧化劑或還原劑的加藥控制。例如，專利文獻3中記載了如下方法：於對原水進行二段RO膜處理時使第一RO供水中存在含有胺磺酸（sulfamic acid）化合物的結合氯系氧化劑，且於第二RO的供水中以使所述ORP成為200 mV～600mV的方式添加還原劑，藉此使第二RO供水中的殘留氧化劑量適當化，於防止第二RO膜裝置中的膜劣化的基礎上利用微生物的殺菌·增殖抑制效果防止膜污染。Previously, dosing control of oxidants or reducing agents based on ORP values was known. For example, Patent Document 3 describes a method in which a combined chlorine-based oxidant containing a sulfamic acid compound is present in the first RO water supply when the raw water is subjected to a two-stage RO membrane treatment, and the water is supplied to the second RO. The reducing agent is added in such a way that the ORP becomes 200 mV to 600 mV, so that the amount of residual oxidant in the second RO water supply is appropriately adjusted, and the microorganism is used for sterilization while preventing the degradation of the film in the second RO film device. · Proliferation inhibition effect prevents membrane fouling.

ORP根據pH值而大幅變動。RO供水通常pH亦於4.5～8.0的範圍內變動。因此，有時即便僅測定ORP並基於所述測定值控制還原劑的添加量，亦無法進行適當的加藥控制。ORP varies greatly depending on the pH. The pH of the RO water supply usually varies within the range of 4.5 to 8.0. Therefore, even if only the ORP is measured and the addition amount of the reducing agent is controlled based on the measured value, appropriate dosing control may not be performed.

專利文獻4中，作為氧化還原反應中的氧化劑或還原劑的添加量的控制方法，記載了如下方法：測定氧化還原反應系統的pH，基於pH的測定值設定ORP的目標值，以成為所述目標ORP值的方式添加控制氧化劑或還原劑。所述方法中，根據作為對象的氧化還原反應的種類，較佳的pH值不同，因此測定反應系統的pH並對每個測定pH值設定作為目標的ORP值。因此，專利文獻4的方法不要求ORP修正值。In Patent Document 4, as a method for controlling the amount of an oxidizing agent or a reducing agent added in a redox reaction, a method is described in which the pH of the redox reaction system is measured, and a target value of ORP is set based on the measured value of the pH so as to become the aforementioned The target ORP value is added in a way that controls the oxidant or reducing agent. In the method, the preferred pH value varies depending on the type of the target redox reaction. Therefore, the pH of the reaction system is measured, and the target ORP value is set for each measured pH value. Therefore, the method of Patent Document 4 does not require an ORP correction value.

專利文獻1：日本專利特開平1-104310號公報
專利文獻2：日本專利特開平1-135506號公報
專利文獻3：日本專利第5099045號公報
專利文獻4：日本專利特開平2-222774號公報Patent Literature 1: Japanese Patent Laid-Open No. 1-104310 Patent Literature 2: Japanese Patent Laid-Open No. 1-135506 Patent Literature 3: Japanese Patent Laid-Open No. 5099045 Patent Literature 4: Japanese Patent Laid-Open No. 2-222774

先前，基於ORP的測定值對氧化劑或還原劑進行加藥控制。但是，由於ORP根據pH值大幅變動，因此僅利用基於ORP的測定值的加藥控制無法進行適當的加藥控制。Previously, dosing control of oxidants or reducing agents was based on the measured values of ORP. However, since the ORP varies greatly depending on the pH value, proper dosing control cannot be performed using only the dosing control based on the measured value of the ORP.

本發明的目的在於提供一種準確掌握並監測及/或控制根據pH值大幅變動的水系統的ORP的方法和裝置、以及利用所述方法和裝置準確地進行氧化劑及/或還原劑的加藥控制的水處理方法和裝置。An object of the present invention is to provide a method and device for accurately grasping and monitoring and / or controlling the ORP of a water system that greatly changes in pH value, and to accurately perform drug addition control of oxidants and / or reducing agents by using the method and device. Water treatment method and device.

本發明者為了解決所述課題而重覆進行了研究，發現藉由基於pH測定值修正ORP測定值，可準確地掌握水系統的ORP。
即，本發明將下述內容作為主旨。The present inventors have repeatedly conducted research in order to solve the above problems, and found that the ORP of the water system can be accurately grasped by correcting the ORP measurement value based on the pH measurement value.
That is, this invention makes the following summary into the summary.

[1]一種水系統的ORP監測·控制方法，其為監測及/或控制水系統的ORP的方法，其測定所述水系統的ORP和pH，基於根據ORP和pH的測定值而預先設定的修正式，將ORP測定值修正為標準狀態下的ORP值，基於所述ORP修正值，對所述水系統的ORP進行監測及/或控制。[1] An ORP monitoring and control method for a water system, which is a method for monitoring and / or controlling the ORP of a water system, and measures the ORP and pH of the water system based on a preset value based on the measured values of the ORP and pH. The correction formula corrects the ORP measurement value to an ORP value in a standard state, and monitors and / or controls the ORP of the water system based on the ORP correction value.

[2]如[1]所述的水系統的ORP監測·控制方法，其中根據ORP和pH的測定值，基於下述式算出ORP修正值；

ORP修正值（mV）=ORP測定值（mV）-59×（7-pH測定值）。[2] The ORP monitoring and control method for a water system according to [1], wherein the ORP correction value is calculated based on the measured values of ORP and pH based on the following formula;

ORP correction value (mV) = ORP measurement value (mV) -59 × (7-pH measurement value).

[3]一種水處理方法，其特徵在於：基於藉由如[1]或[2]所述的水系統的ORP監測·控制方法而求出的ORP修正值，於水系統中添加氧化劑及/或還原劑。[3] A water treatment method, characterized by adding an oxidant to the water system based on the ORP correction value obtained by the ORP monitoring and control method of the water system as described in [1] or [2] Or reducing agent.

[4]如[3]所述的水處理方法，其中以所述ORP修正值成為400 mV～600 mV的方式於所述水系統中添加氧化劑及/或還原劑。[4] The water treatment method according to [3], wherein an oxidizing agent and / or a reducing agent is added to the water system so that the ORP correction value becomes 400 mV to 600 mV.

[5]如[3]或[4]所述的水處理方法，其中於逆滲透膜裝置的被處理水中添加所述氧化劑及/或還原劑。[5] The water treatment method according to [3] or [4], wherein the oxidizing agent and / or reducing agent is added to the water to be treated in the reverse osmosis membrane device.

[6]一種逆滲透膜處理方法，其對添加了游離氯系氧化劑和結合氯系氧化劑或黏泥控制劑的水進行逆滲透膜處理，於所述方法中，基於逆滲透膜供水的ORP值對所述游離氯系氧化劑進行加藥控制，並且基於藉由如[1]或[2]所述的水系統的ORP監測·控制方法而求出的供水的ORP修正值，對所述游離氯系氧化劑進行加藥控制。[6] A reverse osmosis membrane treatment method for performing reverse osmosis membrane treatment on water to which a free chlorine-based oxidant and a combined chlorine-based oxidant or a slime control agent are added. In the method, an ORP value based on a reverse osmosis membrane water supply is performed. Dosing control is performed on the free chlorine-based oxidant, and based on the ORP correction value of the water supply obtained by the ORP monitoring and control method of the water system described in [1] or [2], the free chlorine Department of oxidants for dosing control.

[7]一種水系統的ORP的監測·控制裝置，其為監測及/或控制水系統的ORP的裝置，且包括：ORP測定單元，測定所述水系統的ORP；pH測定單元，測定pH；以及運算單元，基於根據利用所述ORP測定單元所測定的ORP測定值和利用所述pH測定單元所測定的pH測定值而預先設定的修正式，將ORP測定值修正為標準狀態下的ORP值。[7] An ORP monitoring and control device for a water system, which is a device for monitoring and / or controlling the ORP of a water system, and includes: an ORP measurement unit that measures the ORP of the water system; a pH measurement unit that measures the pH; And the calculation unit corrects the ORP measurement value to an ORP value in a standard state based on a correction formula set in advance based on the ORP measurement value measured by the ORP measurement unit and the pH measurement value measured by the pH measurement unit. .

[8]如[7]所述的水系統的ORP的監測·控制裝置，其中所述運算單元是根據ORP及pH測定值並基於下述式算出ORP修正值的單元；

ORP修正值（mV）=ORP測定值（mV）-59×（7-pH測定值）。[8] The ORP monitoring and control device for a water system according to [7], wherein the arithmetic unit is a unit that calculates an ORP correction value based on the ORP and pH measurement values and based on the following formula;

ORP correction value (mV) = ORP measurement value (mV) -59 × (7-pH measurement value).

[9]一種水處理裝置，其特徵在於包括：如[7]或[8]所述的水系統的ORP的監測·控制裝置；以及加藥單元，基於利用所述水系統的ORP的監測·控制裝置的運算單元算出的ORP修正值，將氧化劑及/或還原劑添加於水系統中。[9] A water treatment device, comprising: the monitoring and control device for the ORP of the water system according to [7] or [8]; and a medicating unit based on the monitoring of the ORP of the water system · The ORP correction value calculated by the arithmetic unit of the control device adds an oxidant and / or a reducing agent to the water system.

[10]如[9]所述的水處理裝置，其中所述加藥單元以所述ORP修正值成為400 mV～600 mV的方式於所述水系統中添加氧化劑及/或還原劑。[10] The water treatment device according to [9], wherein the medicating unit adds an oxidizing agent and / or a reducing agent to the water system so that the ORP correction value becomes 400 mV to 600 mV.

[11]如[9]或[10]所述的水處理裝置，其中於逆滲透膜裝置的被處理水中添加所述氧化劑及/或還原劑。[11] The water treatment device according to [9] or [10], wherein the oxidant and / or reducing agent is added to the water to be treated in the reverse osmosis membrane device.

[12]一種水處理裝置，其特徵在於包括：逆滲透膜裝置，對添加了游離氯系氧化劑和結合氯系氧化劑或黏泥控制劑的水進行逆滲透膜處理；加藥控制單元，基於所述逆滲透膜裝置的供水的ORP值對朝所述供水的所述游離氯系氧化劑的添加量進行控制；以及如[7]或[8]所述的水系統的ORP的監測·控制裝置，所述加藥控制單元基於利用所述水系統的ORP的監測·控制裝置而求出的ORP修正值進行游離氯系氧化劑的加藥控制。[12] A water treatment device, comprising: a reverse osmosis membrane device for performing reverse osmosis membrane treatment on water to which a free chlorine-based oxidant and a combined chlorine-based oxidant or a slime control agent are added; The ORP value of the water supply of the reverse osmosis membrane device controls the addition amount of the free chlorine-based oxidant toward the water supply; and the ORP monitoring and control device of the water system according to [7] or [8], The dosing control unit performs dosing control of a free chlorine-based oxidant based on an ORP correction value obtained by an ORP monitoring and control device of the water system.

[發明的效果]
根據本發明，可準確掌握並監測及/或控制根據pH值大幅變動的水系統的ORP。[Effect of the invention]
According to the present invention, it is possible to accurately grasp and monitor and / or control the ORP of a water system that greatly changes in pH.

另外，根據本發明，可利用所述ORP監測·控制方法和裝置準確地進行朝RO供水的氧化劑及/或還原劑的加藥控制。In addition, according to the present invention, the ORP monitoring and control method and device can accurately control the dosing of oxidants and / or reducing agents that supply water to the RO.

以下，對本發明的實施形態進行詳細說明。Hereinafter, embodiments of the present invention will be described in detail.

本發明中，測定水系統的ORP和pH，基於根據ORP和pH的測定值而預先設定的修正式，將ORP的測定值修正為標準狀態下的ORP值，基於所述ORP修正值，對水系統的ORP進行監測及/或控制。In the present invention, the ORP and pH of the water system are measured, and based on a correction formula set in advance based on the measured values of the ORP and pH, the measured value of the ORP is corrected to the ORP value in a standard state, and the water is measured based on the ORP correction value. The ORP of the system is monitored and / or controlled.

即，如上所述，由於水系統的ORP根據pH大幅變動，因此本發明中依據pH測定值修正ORP測定值。That is, as described above, since the ORP of the water system greatly varies depending on the pH, the ORP measurement value is corrected based on the pH measurement value in the present invention.

如後述的實驗例1所示般，若pH增加1，則水系統的ORP測定值變動-59 mV。因此，ORP測定值較佳為依據pH測定值，並利用以下式修正，從而作為pH7的標準狀態下的ORP值而算出。

ORP修正值（mV）=ORP測定值（mV）-59×（7-pH測定值）As shown in Experimental Example 1 described later, when the pH is increased by 1, the ORP measurement value of the water system changes by -59 mV. Therefore, it is preferable that the ORP measurement value is calculated based on the pH measurement value and is corrected by the following formula to be an ORP value in a standard state of pH 7.

ORP correction value (mV) = ORP measurement value (mV) -59 × (7-pH measurement value)

根據本發明的水系統的ORP的監測·控制方法和裝置，於基於ORP測定值向RO供水中添加氧化劑及/或還原劑的RO膜處理的前處理中，可準確地進行氧化劑及/或還原劑的加藥控制。因此，可防止由於氧化劑的過剩添加或用於還原去除過剩的氧化劑的還原劑的添加量不足所導致的RO膜的劣化。另外，可防止由於氧化劑的添加量不足或用於還原氧化劑的還原劑的過剩添加所導致的系統內的黏泥產生·增殖而引起的膜堵塞。藉此，可長期維持穩定運轉。According to the method and device for monitoring and controlling ORP of a water system according to the present invention, it is possible to accurately perform the oxidant and / or reduction in the pretreatment of the RO membrane treatment in which the oxidant and / or the reducing agent is added to the RO water supply based on the ORP measurement value. Dosing control. Therefore, it is possible to prevent deterioration of the RO film due to excessive addition of an oxidant or insufficient addition of a reducing agent for reducing and removing the excessive oxidant. In addition, it is possible to prevent membrane clogging caused by generation and proliferation of slime in the system caused by insufficient addition of an oxidant or excessive addition of a reducing agent for reducing the oxidant. Thereby, stable operation can be maintained for a long time.

於作為RO膜的前處理的氧化劑及/或還原劑的加藥控制中，較佳為以藉由本發明而求出的ORP修正值為規定的範圍內例如作為pH7的ORP修正值成為400 mV～600 mV、尤其是500 mV～600 mV的方式進行加藥控制。In the dosing control of the oxidizing agent and / or reducing agent that is a pre-treatment of the RO membrane, it is preferable that the ORP correction value obtained by the present invention is within a predetermined range, for example, the ORP correction value of pH 7 is 400 mV to Dosing control at 600 mV, especially 500 mV ～ 600 mV.

若所述ORP修正值未滿400 mV，則氧化劑量不足，無法充分防止系統內的黏泥產生、增殖，有可能導致膜污染所引起的膜堵塞。若ORP修正值超過600 mV，則氧化劑量過多，引起金屬材料的腐蝕或膜的氧化劣化，有可能導致脫鹽率的下降等、膜性能的下降。If the ORP correction value is less than 400 mV, the amount of oxidant is insufficient, and the generation and proliferation of slime in the system cannot be fully prevented, which may cause membrane clogging caused by membrane fouling. If the ORP correction value exceeds 600 mV, an excessive amount of oxidant may cause corrosion of metal materials or oxidative degradation of the film, which may result in a decrease in the salt rejection rate, and a decrease in film performance.

以下說明將本發明應用於RO膜處理時的較佳條件及較佳態樣。The following describes preferred conditions and aspects when the present invention is applied to RO film processing.

通常，RO膜處理是於原水中添加游離氯系氧化劑後，利用過濾器等的前處理裝置進行除濁·除菌處理。繼而，視需要添加還原劑而將殘留的游離氯系氧化劑的一部分或全部還原去除，並且將添加了結合氯系氧化劑或黏泥控制劑的水作為RO供水向RO膜裝置中供給。Generally, in RO membrane treatment, free chlorine-based oxidant is added to raw water, and then turbidity and sterilization treatment is performed using a pretreatment device such as a filter. Then, if necessary, a reducing agent is added to reduce or remove a part or all of the remaining free chlorine-based oxidant, and the water added with the chlorine-based oxidant or the slime control agent is supplied to the RO membrane device as the RO water supply.

為了於所述RO膜處理中應用本發明的ORP的監測·控制，而設置測定RO供水的pH和ORP的pH測定單元和ORP測定單元。將自該些測定單元輸出的pH和ORP的測定值輸入至運算單元中，算出ORP修正值。以所述ORP修正值成為規定的範圍內（如上所述，所述規定範圍作為pH7的ORP修正值較佳為400 mV～600 mV、尤佳為500 mV～600 mV）的方式將控制信號輸出至氧化劑及/或還原劑的加藥單元中來進行加藥控制。In order to apply the monitoring and control of the ORP of the present invention to the RO membrane treatment, a pH measuring unit and an ORP measuring unit that measure the pH and ORP of the RO water supply are provided. The measured values of pH and ORP output from these measuring units are input to a computing unit to calculate an ORP correction value. The control signal is output in such a manner that the ORP correction value is within a predetermined range (as mentioned above, the ORP correction value of the predetermined range is preferably 400 mV to 600 mV, and particularly preferably 500 mV to 600 mV). Dosing control in the dosing unit of oxidant and / or reducing agent.

於持續在所述條件下進行RO膜處理的情況下，RO膜有可能發生氧化劣化。因此，所述氧化環境（作為pH7的ORP修正值為400 mV～600 mV、較佳為500 mV～600 mV）下的RO膜處理較佳為以每天的處理時間為10分鐘～360分鐘來間歇地進行處理。In a case where the RO film treatment is continued under the above-mentioned conditions, the RO film may be oxidatively deteriorated. Therefore, the RO membrane treatment under the oxidizing environment (the ORP correction value as pH 7 is 400 mV to 600 mV, preferably 500 mV to 600 mV) is preferably intermittent with a daily treatment time of 10 minutes to 360 minutes. To process.

於藉由還原劑的添加來對殘留游離氯系氧化劑進行分解的情況下，還原劑的添加位置只要為游離氯系氧化劑加藥位置的下游側且結合氯系氧化劑或黏泥控制劑的加藥位置的上游側即可。於RO膜裝置前段配置的裝置較佳為藉由於含有游離氯系氧化劑的狀態下通水而抑制黏泥。因此，較佳為於RO膜裝置附近添加還原劑。於在RO膜裝置的前段設置保安過濾器的情況下，較佳為於保安過濾器和RO膜裝置之間將還原劑、結合氯系氧化劑或黏泥控制劑按照該順序添加。In the case where the residual free chlorine-based oxidant is decomposed by the addition of a reducing agent, the addition position of the reducing agent need only be the downstream side of the free chlorine-based oxidant dosing position and a dosing agent incorporating a chlorine-based oxidant or a slime control agent Just upstream of the location. It is preferable that the device arranged at the front stage of the RO membrane device suppresses slime by passing water in a state containing a free chlorine-based oxidant. Therefore, it is preferable to add a reducing agent near the RO membrane device. In the case where a security filter is provided at the front stage of the RO membrane device, it is preferable to add a reducing agent, a combined chlorine-based oxidant, or a slime control agent in this order between the security filter and the RO membrane device.

＜原水＞
供於RO膜處理的被處理水（原水）可列舉用水（自來水、工業用水等）、排水（含有有機物的排水等）等。本發明特別適合於含有容易產生微生物的易生分解性的低分子量有機物的排水的RO膜處理。根據本發明，於黏泥容易產生、增殖的排水的RO膜處理中，適當地進行氧化劑及/或還原劑的加藥控制，於防止RO膜的氧化劣化的基礎上，可確實地防止膜污染。＜ raw water ＞
Examples of the water to be treated (raw water) for RO membrane treatment include water (tap water, industrial water, etc.), and drainage (drainage containing organic matter, etc.). The present invention is particularly suitable for RO membrane treatment of wastewater containing low-molecular-weight organic matter that is prone to biodegradation. According to the present invention, in the RO membrane treatment of drained water that is liable to generate and multiply slime, the oxidizing agent and / or reducing agent is appropriately controlled to prevent the membrane from being oxidatively degraded, and the membrane can be reliably prevented .

＜游離氯系氧化劑＞
作為於原水中添加的游離氯系氧化劑，可列舉：氯氣、二氧化氯、次氯酸或其鹽、亞氯酸或其鹽、氯酸或其鹽、過氯酸或其鹽、氯化異三聚氰酸或其鹽等，但並不限定於該些。作為鹽形式的游離氯系氧化劑，可例示：次氯酸鈉、次氯酸鉀等的次氯酸鹼金屬鹽、次氯酸鈣、次氯酸鋇等的次氯酸鹼土類金屬鹽、亞氯酸鈉、亞氯酸鉀等的亞氯酸鹼金屬鹽、亞氯酸鋇等的亞氯酸鹼土類金屬鹽、亞氯酸鎳等的其他亞氯酸金屬鹽、氯酸銨、氯酸鈉、氯酸鉀等的氯酸鹼金屬鹽、氯酸鈣、氯酸鋇等的氯酸鹼土類金屬鹽等。該些氯系氧化劑可單獨使用一種，亦可組合使用兩種以上。該些中，次氯酸鹽由於操作容易，因此可較佳地使用。＜ Free chlorine-based oxidant ＞
Examples of the free chlorine-based oxidant to be added to raw water include chlorine gas, chlorine dioxide, hypochlorous acid or a salt thereof, chlorous acid or a salt thereof, chloric acid or a salt thereof, perchloric acid or a salt thereof, and chloroisocyanate. Tricyanic acid or a salt thereof is not limited to these. Examples of the free chlorine-based oxidant in the form of a salt include alkali metal salts of hypochlorite such as sodium hypochlorite and potassium hypochlorite, alkaline earth metal salts of hypochlorite such as calcium hypochlorite and barium hypochlorite, sodium chlorite, Alkali metal salts of chlorite such as potassium chlorite, alkaline earth metal salts of chlorite such as barium chlorite, other metal chlorites such as nickel chlorite, ammonium chlorate, sodium chlorate, potassium chlorate, etc. Alkali metal salts such as alkali metal chlorate, calcium chlorate and barium chlorate. These chlorine-based oxidants may be used alone or in combination of two or more. Among these, hypochlorite is preferably used because it is easy to handle.

該些游離氯系氧化劑可以0.3 mg/LasCl2 ～2.0 mg/LasCl2 左右的濃度對原水持續定量添加。就防止RO膜的氧化劣化和膜污染的觀點而言，較佳為定量添加後述的結合氯系氧化劑或黏泥控制劑，且基於RO供水的ORP修正值對游離氯系氧化劑進行加藥控制。於定量添加游離氯系氧化劑的情況下，後述的還原劑基於RO供水的ORP修正值進行加藥控制。These free chlorine-based oxidants can be continuously and quantitatively added to raw water at a concentration of about 0.3 mg / LasCl 2 to 2.0 mg / LasCl 2 . From the viewpoint of preventing oxidative degradation of the RO membrane and membrane fouling, it is preferable to quantitatively add a chlorine-based oxidant or a slime control agent described later, and to control the free chlorine-based oxidant based on the ORP correction value of the RO water supply. When the free chlorine-based oxidant is quantitatively added, the reducing agent described later performs dosing control based on the ORP correction value of the RO water supply.

＜前處理裝置＞
作為RO膜裝置的前處理裝置，可使用一般的重力過濾器、壓力過濾器等的過濾器或除濁膜裝置。除濁膜裝置可為橫流方式的裝置，亦可為總量過濾方式的裝置。＜ Pretreatment device ＞
As a pretreatment device of the RO membrane device, a filter such as a general gravity filter, a pressure filter, or a turbidity removal device can be used. The turbidity removing device may be a cross flow type device or a total filtration type device.

＜還原劑＞
作為還原劑，並無特別限制，可使用亞硫酸氫、硫代硫酸、亞硫酸、硫代乙醇酸及抗壞血酸等的鈉鹽或其他金屬鹽等的一種或兩種以上。作為還原劑，可吹入氫氣。於添加還原劑的情況下，還原劑較佳為基於ORP修正值進行加藥控制。＜ Reducing agent ＞
The reducing agent is not particularly limited, and one or two or more kinds of sodium salts such as hydrogen sulfite, thiosulfuric acid, sulfurous acid, thioglycolic acid, ascorbic acid, and other metal salts can be used. As the reducing agent, hydrogen can be blown. In the case of adding a reducing agent, the reducing agent is preferably controlled based on the ORP correction value.

＜結合氯系氧化劑或黏泥控制劑＞
作為結合氯系氧化劑，較佳為包含氯系氧化劑與胺磺酸化合物者。＜ Combined with chlorine-based oxidant or slime control agent ＞
The combined chlorine-based oxidant is preferably one containing a chlorine-based oxidant and a sulfamic acid compound.

作為氯系氧化劑，可使用所述游離氯系氧化劑的一種或兩種以上，於操作性的方面而言，可較佳地使用次氯酸鹽。As the chlorine-based oxidant, one, two or more of the free chlorine-based oxidants can be used, and in terms of operability, hypochlorite can be preferably used.

作為胺磺酸化合物，可列舉下述通式[1]所表示的化合物或其鹽。Examples of the sulfamic acid compound include a compound represented by the following general formula [1] or a salt thereof.

[化1]



其中，通式[1]中，R1 和R2 分別獨立地為氫或碳數1～8的烴。[Chemical 1]



However, in the general formula [1], R 1 and R 2 are each independently hydrogen or a hydrocarbon having 1 to 8 carbon atoms.

作為所述胺磺酸化合物，例如除了R1 和R2 均為氫的胺磺酸以外，可列舉N-甲基胺磺酸、N,N-二甲基胺磺酸、N-苯基胺磺酸等。於本發明中使用的胺磺酸化合物中，作為所述化合物的鹽，例如可列舉：鈉鹽、鉀鹽等的鹼金屬鹽、鈣鹽、鍶鹽、鋇鹽等的鹼土類金屬鹽、錳鹽、銅鹽、鋅鹽、鐵鹽、鈷鹽、鎳鹽等的其他金屬鹽、銨鹽和胍鹽等。具體而言，可列舉：胺磺酸鈉、胺磺酸鉀、胺磺酸鈣、胺磺酸鍶、胺磺酸鋇、胺磺酸鐵、胺磺酸鋅等。胺磺酸和該些的胺磺酸鹽可單獨使用一種，亦可組合使用兩種以上。Examples of the amine sulfonic acid compound include N-methylamine sulfonic acid, N, N-dimethylamine sulfonic acid, and N-phenylamine in addition to amine sulfonic acid in which R 1 and R 2 are both hydrogen. Sulfonic acid, etc. In the amine sulfonic acid compound used in the present invention, examples of the salt of the compound include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as calcium salts, strontium salts, and barium salts, and manganese. Salts, copper salts, zinc salts, iron salts, cobalt salts, nickel salts, and other metal salts, ammonium salts, and guanidine salts. Specific examples include sodium sulfamate, potassium sulfamate, calcium sulfamate, strontium sulfamate, barium sulfamate, iron sulfamate, zinc sulfamate, and the like. The sulfamic acid and these sulfamic acid salts may be used alone or in combination of two or more.

若將次氯酸鹽等的氯系氧化劑和胺磺酸鹽等的胺磺酸化合物混合，則該些結合而形成氯胺磺酸鹽，使其穩定化，可於水中保持穩定的游離氯濃度。When a chlorine-based oxidant such as hypochlorite and an amine sulfonic acid compound such as amine sulfonate are mixed, these are combined to form chloramine sulfonate, stabilize it, and maintain a stable free chlorine concentration in water. .

氯系氧化劑和胺磺酸化合物的使用比例較佳為相對於氯系氧化劑的有效氯1莫耳，將胺磺酸化合物設為0.5莫耳～5.0莫耳，更佳為設為0.5莫耳～2.0莫耳。The use ratio of the chlorine-based oxidant and the amine sulfonic acid compound is preferably 1 mol to the effective chlorine of the chlorine-based oxidant, and the amine sulfonic acid compound is set to 0.5 mol to 5.0 mol, more preferably 0.5 mol to 2.0 Mor.

就穩定性的方面而言，結合氯系氧化劑較佳為添加氫氧化鈉、氫氧化鉀等的鹼而調整為pH12以上，更佳為調整為pH13以上。In terms of stability, the combined chlorine-based oxidant is preferably adjusted to pH 12 or higher by adding an alkali such as sodium hydroxide or potassium hydroxide, and more preferably adjusted to pH 13 or higher.

結合氯系氧化劑較佳為例如設為如下所述的調配。
（A）一種pH≧12的水溶液，其包含有效氯濃度1重量%～8重量%、較佳為3重量%～6重量%的氯系氧化劑、和1.5重量%～9重量%、較佳為4.5重量%～8重量%的胺磺酸化合物。
（B）一種pH≧12的水溶液，其於所述（A）中進一步包含0.05重量%～3.0重量%的唑類、1.5重量%～3.0重量%的陰離子性聚合物、0.5重量%～4.0重量%的膦酸類的一種或兩種以上。The chlorine-based oxidizing agent is preferably prepared, for example, as described below.
(A) An aqueous solution having a pH ≧ 12, which contains an effective chlorine concentration of 1 to 8% by weight, preferably 3 to 6% by weight of a chlorine-based oxidant, and 1.5 to 9% by weight, preferably 4.5 to 8% by weight of the sulfamic acid compound.
(B) an aqueous solution having a pH ≧ 12, further comprising 0.05 to 3.0% by weight of azoles, 1.5 to 3.0% by weight of anionic polymer, and 0.5 to 4.0% by weight in (A) % Of one or two or more phosphonic acids.

於所述（A）、（B）中，pH藉由鹼劑的添加而進行調整。In (A) and (B), the pH is adjusted by adding an alkali agent.

該些結合氯系氧化劑可單獨使用一種，亦可組合使用兩種以上。These combined chlorine-based oxidants may be used alone or in combination of two or more.

結合氯系氧化劑較佳為以成為0.3 mg/LasCl2 ～1.0 mg/LasCl2 左右的濃度的方式持續定量添加。The combined chlorine-based oxidant is preferably continuously and quantitatively added so as to have a concentration of about 0.3 mg / LasCl 2 to 1.0 mg / LasCl 2 .

本發明中，代替所述結合氯系氧化劑，作為抑制微生物活動的藥劑，亦可添加例如亞甲基雙硫代氰酸酯（Methylene Bisthiocyanate，MBT）、2,2-二溴-3-氮基丙醯胺（dibromo nitrilopropionamide，DBNPA）、2,2-二溴-2-硝基乙醇（dibromo nitroethanol，DBNE）、雙-1,4-溴乙醯氧基-2-丁烯（bis bromoacetoxy butene，BBAB）、5-氯-2-甲基-4-異噻唑啉-3-酮（5-chloro-2-methyl-4-isothiazoline-3-one，MIT）、二硫醇（4,5-二氯-1,2-二硫雜環戊烷-3-酮）、5-氯-2,4,6-三氟間苯二甲腈（5-chloro-2,4,6-trifluoroisophthalonitrile，CFIPN）、六溴二甲基碸（hexabromodimethyl sulfone，HBDS）、3,3,4,4-四氯四氫噻吩-1,1-二氧化物（3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide，TCS）、2-溴-2-硝基丙烷-1,3-二醇（2-bromo-2-nitropropane-1,3-diol，BNP）、苯并異噻唑啉-3-酮（benzoisothiazoline-3-one，BIT）、戊二醛（gultaraldehyde，GA）等的黏泥控制劑的一種或兩種以上。亦可併用添加所述結合氯系氧化劑與黏泥控制劑。In the present invention, instead of the combined chlorine-based oxidant, as a medicine for suppressing microbial activity, for example, Methylene Bisthiocyanate (MBT), 2,2-dibromo-3-nitro group may be added. Dibromo nitrilopropionamide (DBNPA), 2,2-dibromo nitroethanol (DBNE), bis-1,4-bromoacetoxy-2-butene (bis bromoacetoxy butene, BBAB), 5-chloro-2-methyl-4-isothiazoline-3-one (MIT), dithiol (4,5-di Chloro-1,2-dithiacyclopentane-3-one), 5-chloro-2,4,6-trifluoroisophthalonitrile (CFIPN) , Hexabromodimethyl sulfone (HBDS), 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide (3,3,4,4-tetrachlorotetrahydrothiophene-1,1- dioxide (TCS), 2-bromo-2-nitropropane-1,3-diol (2-bromo-2-nitropropane-1,3-diol, BNP), benzoisothiazoline-3-one (benzoisothiazoline -3-one (BIT), gultaraldehyde (GA) and other slime control agents . The combined chlorine-based oxidant and the slime control agent may be added in combination.

＜pH測定單元·ORP測定單元＞
作為pH測定單元、ORP測定單元，並無特別限制，可使用一般的pH計、ORP計。<PH measurement unit and ORP measurement unit>
The pH measurement unit and ORP measurement unit are not particularly limited, and a general pH meter or ORP meter can be used.

為了測定RO供水的pH及ORP，pH計和ORP計較佳為設置於RO膜裝置的正前方（供水入口部）。In order to measure the pH and ORP of the RO water supply, the pH meter and the ORP meter are preferably provided directly in front of the RO membrane device (water supply inlet).

＜RO膜裝置＞
RO膜裝置是由將具備RO膜（包含奈米過濾（Nanofiltration，NF）膜）的RO膜元件裝填於容器（vessel）中而成的RO膜模組構成。本發明中使用的RO膜是在高濃度側施加介隔膜的溶液間的滲透壓差以上的壓力，阻止溶質而透過溶媒的液體分離膜。作為RO膜的膜結構，可列舉複合膜、相分離膜等的高分子膜等。作為應用於本發明的RO膜的素材，例如可列舉芳香族系聚醯胺、脂肪族系聚醯胺、該些的複合材料等的聚醯胺系素材等。RO膜模組的形式並無特別限制，例如可應用管狀膜模組、平面膜模組、螺旋膜模組、中空絲膜模組等。<RO membrane device>
The RO membrane device includes an RO membrane module in which a RO membrane element including an RO membrane (including a nanofiltration (NF) membrane) is packed in a container. The RO membrane used in the present invention is a liquid separation membrane in which a pressure equal to or greater than the osmotic pressure difference between the solutions of the dielectric membrane is applied to the high-concentration side, and the solute is prevented from permeating through the solvent. Examples of the membrane structure of the RO membrane include polymer membranes such as composite membranes and phase separation membranes. Examples of the material used in the RO film of the present invention include aromatic polyamides, aliphatic polyamines, and polyamide materials such as these composite materials. The form of the RO membrane module is not particularly limited. For example, a tubular membrane module, a flat membrane module, a spiral membrane module, a hollow fiber membrane module, and the like can be applied.

本發明中的RO膜裝置的較佳運轉條件如下所述。
（1）RO濃縮水量：3.6 m3 /h以上、例如3.6 m3 /h～7.0 m3 /h
（2）RO膜規格：
標準壓力=0.735 MPa的超低壓膜
RO膜面積=35 m2 ～41 m2
初期純水通量=1.0 m/d（25℃、0.735 MPa）以上
初期脫鹽率=98%以上。
（3）回收率：通常50%～80%（以濃縮水的朗格利（Langelier）指數為0以下、濃縮水的二氧化矽濃度成為溶解度以下的方式設定）The preferable operating conditions of the RO membrane device in the present invention are as follows.
(1) RO water and concentrated: 3.6 m 3 / h or more, for example 3.6 m 3 /h~7.0 m 3 / h
(2) RO film specifications:
Ultra-low pressure membrane with standard pressure = 0.735 MPa
RO membrane area = 35 m 2 to 41 m 2
Initial pure water flux = 1.0 m / d (25 ° C, 0.735 MPa) or more. Initial desalination rate = 98% or more.
(3) Recovery rate: usually 50% to 80% (set in such a way that the Langelier index of the concentrated water is 0 or less and the concentration of silicon dioxide in the concentrated water is less than the solubility)

＜後段裝置＞
可於所述RO膜裝置的後段視需要設置電脫離子裝置或離子交換裝置來進一步提高處理水的水質。
[實施例]＜ Back-end device ＞
An electric deionization device or an ion exchange device may be provided at the rear stage of the RO membrane device as needed to further improve the water quality of the treated water.
[Example]

以下，列舉實驗例、實施例和比較例對本發明進行更具體的說明。Hereinafter, the present invention will be described more specifically with reference to experimental examples, examples, and comparative examples.

＜實驗例1＞
藉由於純水中添加硫酸或氫氧化鈉，製備pH不同的試驗水，分別測定ORP，並調查pH與ORP的關係。將水溫設為25℃。將結果示於圖1中。＜ Experimental Example 1 ＞
Test water with different pH was prepared by adding sulfuric acid or sodium hydroxide to pure water, and ORP was measured separately, and the relationship between pH and ORP was investigated. The water temperature was set to 25 ° C. The results are shown in FIG. 1.

根據圖1，可知若pH變動1，則ORP變動-59 mV。From FIG. 1, it can be seen that if the pH changes by 1, the ORP changes by -59 mV.

[生物污垢抑制試驗]
＜實施例1＞
將於純水（RO處理水水質水準）中添加了作為生化需氧量（Biochemical Oxygen Demand，BOD）源的乙醇3 mg/LasC、作為N源的氯化銨0.2 mg/L、作為P源的磷酸二氫鈉20 μg/L左右的水作為供水，實施保安過濾器通水試驗。
保安過濾器使用孔徑10 μm的繞線過濾器，以2 L/min的流量通水。[Biofouling suppression test]
<Example 1>
Add 3 mg / LasC of ethanol as the source of Biochemical Oxygen Demand (BOD), 0.2 mg / L of ammonium chloride as the source of N, and P as the source of pure water (RO treated water). Water of about 20 μg / L of sodium dihydrogen phosphate was used as a water supply, and a water filter test was performed on the security filter.
The security filter uses a wire-wound filter with a pore size of 10 μm and passes water at a flow rate of 2 L / min.

於所述供水中持續添加0.6 mg/LasCl2 的氯胺磺酸鈉作為結合氯系氧化劑，並且以使ORP修正值一天一次連續360分鐘成為600 mV的方式添加次氯酸鈉作為游離氯系氧化劑。To the water supply, 0.6 mg / LasCl 2 of sodium chloramine sulfonate was continuously added as a combined chlorine-based oxidant, and sodium hypochlorite was added as a free chlorine-based oxidant so that the ORP correction value became 600 mV for 360 consecutive minutes once a day.

ORP修正值藉由如下方式求出：根據在保安過濾器入口測定的供水的ORP值與pH值，基於圖1所示的關係，藉由下述式算出pH7的標準狀態下的ORP值。

ORP修正值（mV）=供水的ORP測定值（mV）-59×（7-供水的pH測定值）The ORP correction value is obtained by calculating the ORP value in the standard state of pH 7 based on the relationship shown in FIG. 1 from the ORP value and pH value of the water supply measured at the entrance of the security filter, based on the relationship shown in FIG. 1.

ORP correction value (mV) = ORP measurement value of water supply (mV) -59 × (7-pH measurement value of water supply)

關於保安過濾器的供水的pH，進行pH調整而在6.0～7.0的中性區域的範圍內變動。Regarding the pH of the water supplied to the security filter, the pH was adjusted to vary within a neutral range of 6.0 to 7.0.

調查通水開始初期、通水100 h後、通水120 h後的各自的保安過濾器的差壓，將結果示於表1中。The differential pressures of the respective security filters at the initial stage of the start of water flow, after 100 hours of water flow, and after 120 hours of water flow were investigated, and the results are shown in Table 1.

＜比較例1＞
實施例1中，並未利用pH的測定值修正ORP的測定值，直接使用所測定的ORP值，以所述ORP測定值成為600 mV的方式添加游離氯系氧化劑，除此以外同樣地進行通水試驗。將結果示於表1中。〈Comparative example 1〉
In Example 1, the measured value of ORP was not corrected using the measured value of pH, the measured ORP value was used directly, and a free chlorine-based oxidant was added so that the measured value of ORP became 600 mV. Water test. The results are shown in Table 1.

＜參考例1＞
實施例1中，不添加結合氯系氧化劑及游離氯系氧化劑，除此以外同樣地進行通水試驗。將結果示於表1中。此時的保安過濾器供水的修正ORP值為250 mV左右。＜ Reference Example 1 ＞
Except that the combined chlorine-based oxidant and free chlorine-based oxidant were not added in Example 1, a water passing test was performed in the same manner. The results are shown in Table 1. The corrected ORP value of the security filter water supply at this time is about 250 mV.

＜參考例2＞
實施例1中，僅將結合氯系氧化劑0.6 mg/LasCl2 設為持續添加，不添加游離氯系氧化劑，除此以外同樣地進行通水試驗。將結果示於表1中。此時的保安過濾器供水的修正ORP值為300 mV左右。＜ Reference Example 2 ＞
In Example 1, a continuous water test was performed in the same manner except that the combined chlorine-based oxidant 0.6 mg / LasCl 2 was continuously added, and no free chlorine-based oxidant was added. The results are shown in Table 1. The corrected ORP value of the security filter water supply at this time is about 300 mV.

＜參考例3＞
實施例1中，以0.8 mg/LasCl2 僅持續添加游離氯系氧化劑，不添加結合氯系氧化劑，除此以外同樣地進行通水試驗。將結果示於表1中。此時的保安過濾器供水的修正ORP值為650 mV左右。＜ Reference Example 3 ＞
In Example 1, a water-permeability test was performed in the same manner except that only a free chlorine-based oxidant was continuously added at 0.8 mg / LasCl 2 and no bonded chlorine-based oxidant was added. The results are shown in Table 1. The corrected ORP value of the security filter water supply at this time is about 650 mV.

[表1]

[Table 1]

根據表1明確，於基於根據pH測定值而修正的ORP值進行游離氯系氧化劑的加藥控制的實施例1中，可防止黏泥的產生所引起的過濾器的污染、污染所引起的差壓的上升。It is clear from Table 1 that in Example 1 where dosing control of free chlorine-based oxidant is performed based on the ORP value corrected based on the pH measurement value, it is possible to prevent filter pollution caused by the generation of slime, and the difference caused by pollution. The pressure rises.

相對於此，於並未利用pH值修正ORP測定值而進行加藥控制的比較例1中，產生游離氯系氧化劑的過量或不足，差壓上升。On the other hand, in Comparative Example 1 in which the dosing control was performed without using the pH value to correct the ORP measurement value, an excess or deficiency of the free chlorine-based oxidant occurred, and the differential pressure increased.

於未添加氧化劑的參考例1中，於早期差壓上升。於僅添加氧化力低的結合氯系氧化劑的參考例2中，差壓亦上升。In Reference Example 1 to which no oxidizing agent was added, the differential pressure increased at an early stage. In Reference Example 2 in which only a chlorine-based oxidizing agent having a low oxidation power was added, the differential pressure also increased.

認為該些比較例1和參考例1、參考例2中，無法防止供水系統內的黏泥的產生，由於過濾器的污染差壓上升。It is considered that in these Comparative Examples 1 and Reference Examples 1 and 2, the generation of slime in the water supply system could not be prevented, and the differential pressure due to the pollution of the filter increased.

參考例3中不存在差壓上升的問題，但存在游離氯系氧化劑的過剩添加所引起的假定了過濾器或實機時的RO膜劣化之虞。In Reference Example 3, there is no problem in that the differential pressure rises, but there is a possibility that the RO membrane at the time of a filter or an actual machine may deteriorate due to the excessive addition of a free chlorine-based oxidant.

[RO膜劣化試驗]
＜實施例2＞
於進行了殘留氯去除的自來水中，添加0.6 mg/LasCl2 的氯胺磺酸鹽系結合氯系氧化劑。其後，與實施例1同樣地，以使修正後的ORP值一天一次連續360分鐘成為600 mV的方式添加次氯酸鈉作為游離氯系氧化劑。使用所述水作為RO供水，實施RO平膜試驗。作為RO膜，使用一般的超低壓膜。以回收率75%、運轉通量0.66 m/d通水，調查通水開始時與通水120 h後的脫鹽率（=[1-處理水水質/{（供水水質+濃縮水水質）/2}]×100 此處水質是指導電率），將結果示於表2中。[RO film deterioration test]
<Example 2>
In tap water from which residual chlorine was removed, 0.6 mg / LasCl 2 of a chloramine sulfonate-based combined chlorine-based oxidant was added. Thereafter, as in Example 1, sodium hypochlorite was added as a free chlorine-based oxidant so that the corrected ORP value became 600 mV for 360 minutes continuously once a day. The RO flat film test was performed using the water as the RO water supply. As the RO film, a general ultra-low pressure film is used. At a recovery rate of 75% and an operating flux of 0.66 m / d, the rate of desalination at the beginning of the pass and 120 h after the pass was investigated (= [1-treated water quality / {(water supply quality + concentrated water quality) / 2) }] × 100 where the water quality is the guide rate), and the results are shown in Table 2.

試驗中，RO供水的pH於6.0～7.0的中性區域中變動。In the test, the pH of the RO water supply fluctuated in a neutral region of 6.0 to 7.0.

＜比較例2＞
實施例2中，並未利用pH的測定值修正ORP的測定值，直接使用所測定的ORP值，以所述ORP值成為600 mV的方式添加游離氯系氧化劑，除此以外同樣地進行通水試驗。將結果示於表2中。〈Comparative example 2〉
In Example 2, the measured value of the ORP was not corrected using the measured value of pH, and the measured value of the ORP was used directly, and a free chlorine-based oxidant was added so that the ORP value became 600 mV, and water was passed through in the same manner. test. The results are shown in Table 2.

＜參考例4＞
實施例2中，不添加結合氯系氧化劑，以修正ORP值成為700 mV的方式僅添加游離氯系氧化劑，除此以外同樣地進行通水試驗。將結果示於表2中。＜ Reference Example 4 ＞
In Example 2, a water-passing test was performed in the same manner except that only the free chlorine-based oxidant was added so that the combined ORP value was 700 mV without adding a combined chlorine-based oxidant. The results are shown in Table 2.

[表2]

[Table 2]

根據表2明確，基於根據pH測定值而修正的ORP值進行了游離氯系氧化劑的加藥控制。於實施例2中，不存在RO膜劣化的問題，因此幾乎不存在脫鹽率的下降。It is clear from Table 2 that the dosing control of the free chlorine-based oxidant was performed based on the ORP value corrected based on the pH measurement value. In Example 2, since there was no problem of deterioration of the RO film, there was almost no decrease in the salt rejection rate.

相對於此，於並未利用pH值修正ORP測定值而進行加藥控制的比較例2中，產生游離氯系氧化劑的過量或不足，但幾乎未觀察到脫鹽率的下降。On the other hand, in Comparative Example 2 in which the dosing control was performed without using the pH value to correct the ORP measurement value, an excess or deficiency of the free chlorine-based oxidant was generated, but a decrease in the salt rejection rate was hardly observed.

參考例4中，由於游離氯系氧化劑的過剩添加所引起的RO膜劣化，脫鹽率下降。In Reference Example 4, the RO membrane deteriorated due to the excessive addition of a free chlorine-based oxidant, and the salt rejection rate decreased.

使用特定的態樣對本發明進行詳細的說明，但對於所屬技術領域中具有通常知識者而言明確可不脫離本發明的意圖與範圍而進行各種變更。
本申請案基於2018年3月22日提出申請的日本專利申請2018-054655，將其整體藉由引用而援用。Although this invention is demonstrated in detail using a specific aspect, it is clear to those skilled in the art that various changes can be made without deviating from the meaning and scope of this invention.
This application is based on Japanese Patent Application No. 2018-054655 filed on March 22, 2018, which is incorporated by reference in its entirety.

無no

圖1是表示實驗例1的結果的圖表。FIG. 1 is a graph showing the results of Experimental Example 1. FIG.

Claims (12)

一種水系統的氧化還原電位監測·控制方法，其為監測及/或控制水系統的氧化還原電位的方法，其測定所述水系統的氧化還原電位和pH，基於根據氧化還原電位和pH的測定值而預先設定的修正式，將氧化還原電位測定值修正為標準狀態下的氧化還原電位值，基於所述氧化還原電位修正值，對所述水系統的氧化還原電位進行監測及/或控制。A redox potential monitoring and control method for a water system is a method for monitoring and / or controlling a redox potential of a water system, which measures the redox potential and pH of the water system based on the measurement based on the redox potential and pH In the correction formula set in advance, the measured redox potential is corrected to a redox potential value in a standard state, and the redox potential of the water system is monitored and / or controlled based on the redox potential correction value. 如申請專利範圍第1項所述的水系統的氧化還原電位監測·控制方法，其中根據氧化還原電位和pH的測定值，基於下述式算出氧化還原電位修正值； 氧化還原電位修正值（mV）=氧化還原電位測定值（mV）-59×（7-pH測定值）。The redox potential monitoring and control method for a water system according to item 1 of the scope of the patent application, wherein the redox potential correction value is calculated based on the following formula based on the measured redox potential and pH measurement value; Corrected value of redox potential (mV) = measured value of redox potential (mV)-59 x (7-pH measured value). 一種水處理方法，其特徵在於：基於藉由如申請專利範圍第1項或第2項所述的水系統的氧化還原電位監測·控制方法而求出的氧化還原電位修正值，於水系統中添加氧化劑及/或還原劑。A water treatment method, characterized in that, based on a redox potential correction value obtained by a redox potential monitoring and control method for a water system as described in item 1 or 2 of a patent application scope, a water system is used in a water system. Add oxidants and / or reducing agents. 如申請專利範圍第3項所述的水處理方法，其中以所述氧化還原電位修正值成為400 mV～600 mV的方式於所述水系統中添加氧化劑及/或還原劑。The water treatment method according to item 3 of the scope of patent application, wherein an oxidizing agent and / or a reducing agent is added to the water system in such a manner that the redox potential correction value becomes 400 mV to 600 mV. 如申請專利範圍第3項或第4項所述的水處理方法，其中於逆滲透膜裝置的被處理水中添加所述氧化劑及/或還原劑。The water treatment method according to item 3 or item 4 of the scope of patent application, wherein the oxidant and / or reducing agent is added to the treated water of the reverse osmosis membrane device. 一種逆滲透膜處理方法，其對添加了游離氯系氧化劑和結合氯系氧化劑或黏泥控制劑的水進行逆滲透膜處理，於所述逆滲透膜處理方法中， 基於逆滲透膜供水的氧化還原電位值對所述游離氯系氧化劑進行加藥控制，並且 基於藉由如申請專利範圍第1項或第2項所述的水系統的氧化還原電位監測·控制方法而求出的供水的氧化還原電位修正值，對所述游離氯系氧化劑進行加藥控制。A reverse osmosis membrane treatment method for performing reverse osmosis membrane treatment on water to which a free chlorine-based oxidant and a combined chlorine-based oxidant or a slime control agent are added. In the reverse osmosis membrane treatment method, Dosing control the free chlorine-based oxidant based on the redox potential value of the reverse osmosis membrane water supply, and Dosing control of the free chlorine-based oxidant based on the redox potential correction value of the water supply obtained by the redox potential monitoring and control method of the water system according to the first or second patent application scope. . 一種水系統的氧化還原電位的監測·控制裝置，其為監測及/或控制水系統的氧化還原電位的裝置，且包括：氧化還原電位測定單元，測定所述水系統的氧化還原電位；pH測定單元，測定pH；以及運算單元，基於根據利用所述氧化還原電位測定單元所測定的氧化還原電位測定值和利用所述pH測定單元所測定的pH測定值而預先設定的修正式，將氧化還原電位測定值修正為標準狀態下的氧化還原電位值。A redox potential monitoring and control device for a water system is a device for monitoring and / or controlling a redox potential of a water system, and includes: a redox potential measuring unit for measuring the redox potential of the water system; pH measurement A unit for measuring pH; and a calculation unit for redoxing based on a preset correction formula based on a redox potential measurement value measured by the redox potential measurement unit and a pH measurement value measured by the pH measurement unit. The measured potential value is corrected to the redox potential value in the standard state. 如申請專利範圍第7項所述的水系統的氧化還原電位的監測·控制裝置，其中所述運算單元是根據氧化還原電位和pH測定值並基於下述式算出氧化還原電位修正值的單元； 氧化還原電位修正值（mV）=氧化還原電位測定值（mV）-59×（7-pH測定值）。The redox potential monitoring and control device for a water system according to item 7 of the scope of the patent application, wherein the arithmetic unit is a unit for calculating the redox potential correction value based on the redox potential and the pH measurement value and based on the following formula; Corrected value of redox potential (mV) = measured value of redox potential (mV)-59 x (7-pH measured value). 一種水處理裝置，其特徵在於包括：如申請專利範圍第7項或第8項所述的水系統的氧化還原電位的監測·控制裝置；以及加藥單元，基於利用所述水系統的氧化還原電位的監測·控制裝置的運算單元算出的氧化還原電位修正值，將氧化劑及/或還原劑添加於水系統中。A water treatment device, comprising: a monitoring and control device for a redox potential of a water system according to item 7 or 8 of a patent application scope; and a dosing unit based on using the redox of the water system The redox potential correction value calculated by the arithmetic unit of the potential monitoring and control device adds an oxidant and / or a reducing agent to the water system. 如申請專利範圍第9項所述的水處理裝置，其中所述加藥單元以所述氧化還原電位修正值成為400 mV～600 mV的方式於所述水系統中添加氧化劑及/或還原劑。The water treatment device according to item 9 of the scope of the patent application, wherein the dosing unit adds an oxidant and / or a reducing agent to the water system in such a manner that the redox potential correction value becomes 400 mV to 600 mV. 如申請專利範圍第9項或第10項所述的水處理裝置，其中於逆滲透膜裝置的被處理水中添加所述氧化劑及/或還原劑。The water treatment device according to item 9 or 10 of the scope of application for a patent, wherein the oxidant and / or reducing agent is added to the treated water of the reverse osmosis membrane device. 一種水處理裝置，其特徵在於包括：逆滲透膜裝置，對添加了游離氯系氧化劑和結合氯系氧化劑或黏泥控制劑的水進行逆滲透膜處理；加藥控制單元，基於所述逆滲透膜裝置的供水的氧化還原電位值對朝所述供水的所述游離氯系氧化劑的添加量進行控制；以及如申請專利範圍第7項或第8項所述的水系統的氧化還原電位的監測·控制裝置，所述加藥控制單元基於利用所述水系統的氧化還原電位的監測·控制裝置而求出的氧化還原電位修正值進行游離氯系氧化劑的加藥控制。A water treatment device, comprising: a reverse osmosis membrane device that performs reverse osmosis membrane treatment on water to which a free chlorine-based oxidant and a combined chlorine-based oxidant or a slime control agent are added; and a dosing control unit based on the reverse osmosis The oxidation-reduction potential value of the water supply of the membrane device controls the amount of the free chlorine-based oxidant added to the water supply; and the monitoring of the oxidation-reduction potential of the water system according to item 7 or 8 of the scope of patent application A control device, wherein the dosing control unit performs dosing control of the free chlorine-based oxidant based on the redox potential correction value obtained by the monitoring-control device of the redox potential of the water system.
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